EP0530959B1 - Compositions adoucissantes pour le linge à base d'un composé de pentaérythritol et d'un agent dispersant pour un tel composé - Google Patents

Compositions adoucissantes pour le linge à base d'un composé de pentaérythritol et d'un agent dispersant pour un tel composé Download PDF

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Publication number
EP0530959B1
EP0530959B1 EP92306451A EP92306451A EP0530959B1 EP 0530959 B1 EP0530959 B1 EP 0530959B1 EP 92306451 A EP92306451 A EP 92306451A EP 92306451 A EP92306451 A EP 92306451A EP 0530959 B1 EP0530959 B1 EP 0530959B1
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EP
European Patent Office
Prior art keywords
pentaerythritol
fabric softening
pec
composition
detergent
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EP92306451A
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German (de)
English (en)
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EP0530959A1 (fr
Inventor
Eduardo E. Puentes-Bravo
Jean-Paul Mhf Grandmaire
Anita M. Hermosilla
Viviane E. A. Tack
Jan R. P. Doms
Pierre M. Lambert
Marcel Jeg Gillis
Paul A. Heckles
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Colgate Palmolive Co
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Colgate Palmolive Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/047—Arrangements specially adapted for dry cleaning or laundry dryer related applications
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates

Definitions

  • This invention relates to fabric softening compositions for application to laundry during washing to apply to the fibers of the fabrics of such laundry fabric softening amounts of fabric softening components of the compositions. More particularly, it relates to such products that include as fabric softening components higher fatty acid esters of pentaerythritol, of pentaerythritol oligomers, or of alkoxylated derivatives thereof, all of which may be designated PEC (for pentaerythritol compound), together with a dispersing agent for such PEC, such as a clay or an emulsifier and which do not essentially contain quaternary ammonium salts.
  • PEC for pentaerythritol compound
  • Fabric softening compositions and articles have long been employed to make washed laundry items softer to the touch and more comfortable to the wearer.
  • Such compositions include solutions, emulsions and particulate and powder products, and such articles include paper strips and sponges that have been impregnated with fabric softener.
  • the fabric softeners of choice for most commercial products have usually been quaternary ammonium salts, such as dimethyl ditallowyl ammonium chloride, and emulsions of such softener have been added to the rinse water in the washing machine to effectively soften laundry.
  • such emulsions or powder products including such fabric softener can be added to the wash water, with a detergent composition, or the detergent composition can include a fabric softening components, making it a so-called "softergent”.
  • a fabric softening component such as a quaternary ammonium salt, may be added to the automatic laundry dryer wherein, during tumbling of the laundry in a heated environment, the fabric softener is applied to the laundry by repeated contact, and softens it.
  • such quaternary ammonium salt is a di-lower alkyl, di-higher alkyl ammonium halide but mono-lower alkyl tri-higher alkyl ammonium halides have also found use in some instances.
  • EP-A-494769 is only citable under EPC Article 54(3). It discloses a dispersion in water of 20 parts clay (gel forming sodium bentonite), 2 parts tripentaerythritol tetralaurate, 2 parts optional emulsifier, and 76 parts water. This liquid may be mixed with liquid detergent composition for use in the washing step.
  • US-A-4128484 discloses a rinse-added softening composition
  • a rinse-added softening composition comprising a fatty acid partial ester of a polyhydric alcohol as softener and a cationic surfactant.
  • JP-A-2047362 discloses and teaches three component compositions containing
  • EP-A-243735 discloses compositions containing 1 to 15% of quaternary ammonium compound with specific constituent group and 0.5 to 5% of a carboxylic acid ester, the ratio of the quat to the ester being 10:1 to 1:1.
  • the examples of this document use glycerin monostearate as the ester.
  • a fabric softening built detergent composition for application to fibrous materials, so that a fabric softening component thereof is deposited on the fibrous materials and softens them, comprises a PEC, which is a fabric softening component which is a C 8 -C 24 aliphatic acid ester of pentaerythritol, of an oligomer of pentaerythritol, of a lower alkylene oxide derivative, containing 1 to 10 alkylene oxide moieties, of pentaerythritol or of a lower alkylene oxide derivative, containing 1 to 10 alkylene oxide moieties, of an oligomer of pentaerythritol, or a mixture thereof, a dispersing agent for the PEC, a synthetic organic detergent, and a detergent builder which composition is essentially free of quaternary ammonium compound fabric softener, or other quaternary ammonium compounds, the dispersing agent being an emulsifier or
  • PECs those which are preferred are the pentaerythritol distearates and dipentaerythritol dilaurates, and of the dispersing agents those preferred are ethoxylated amines or alkanolamines which are positively charged at acidic pHs, such as 2.5-4, or montmorillonites, such as sodium, calcium and potassium bentonites.
  • the invention also includes processes for softening laundry with the invented compositions.
  • composition may also comprise an anionic or nonionic synthetic organic detergent or a mixture thereof.
  • the invention in the form of an aqueous liquid composition preferably contains 3-15% of detergent, 5-25% of builder, 0.5 to 15% of adjuvant(s), 3 to 15% of PEC and 3 to 30% of emulsifier.
  • the invention in the form of a particulate composition preferably contains 3 to 35% of detergent, 10 to 80% of builder, 0.5 to 25% of adjuvant(s), 2 to 15% of PEC and 5 to 30% of fabric softening clay.
  • the dispersant is a fabric softening clay and no quaternary ammonium compound is present.
  • U.S. patent 3,928,212 describes various softening agents which are polyhydric alcohol esters but none of them is a pentaerythritol ester or an ester of an oligomer or ethoxylated derivative of pentaerythritol or of an oligomer thereof.
  • U.S. patent 4,126,562 mentions erythritol and pentaerythritol in a list of alcohols which may be reacted with higher fatty acids to produce fabric conditioning agents but no such compound is actually described and none is shown in a fabric softening composition or article. Also U.S.
  • patent 4,126,562 is for a combination of a quaternary ammonium salt fabric softener and a nonionic ester of an alcohol with a higher fatty acid, and there is no teaching that the ester would be useful alone as a fabric softener.
  • U.S. patent 4,142,978 describes sorbitan esters with phase modifying components, such as alkyl sulfates, on a dryer sheet for softening laundry while it is being tumble dried in an automatic laundry dryer. The patent does not mention any pentaerythritol esters.
  • patent 4,162,984 relates to a textile treatment emulsion of a water insoluble cationic fabric softener, which is preferably a quaternary ammonium salt or an alkylimidazolinium salt, with a water insoluble nonionic fabric softener, which is preferably a fatty acid ester of a mono- or polyhydric alcohol or an anhydride thereof, and an aromatic mono-or dicarboxylic acid.
  • a water insoluble cationic fabric softener which is preferably a quaternary ammonium salt or an alkylimidazolinium salt
  • a water insoluble nonionic fabric softener which is preferably a fatty acid ester of a mono- or polyhydric alcohol or an anhydride thereof, and an aromatic mono-or dicarboxylic acid.
  • polyhydric alcohols that may be esterified, according to the patent, is pentaerythritol, but no pentaerythritol ester is described specifically nor is any oligomer of pentaerythritol suggested, and none is shown to be a useful fabric softening agent in the absence of quaternary ammonium salt and aromatic carboxylic acid.
  • polyglycerol is a polyhydric alcohol, as is pentaerythritol, it is not the same as pentaerythritol and the patent does not suggest the use of applicants' pentaerythritol esters as fabric softeners.
  • European patent specification 276999-A mentions fabric conditioning compositions that contain a non-cationic fabric softener and a nonionic cellulose ether.
  • esters of polyhydric alcohols are mentioned as suitable conditioning agents, pentaerythritol esters are not disclosed.
  • German patent specification 3612479-A describes textile softening compositions that contain quaternary ammonium compounds with carboxylic esters, and among the carboxylic acid esters are mentioned esters of various alcohols and polyols, including pentaerythritol. However, no such specific ester is described or even named, and no softening composition which does not contain quaternary ammonium compound as the fabric softener is disclosed.
  • Japanese patent 90 47,370 discloses fabric softening compositions that are based on quaternary ammonium salts but may contain higher fatty acid ester of pentaerythritol. No specific such ester is described in the abstract.
  • any pentaerythritol ester could be employed with a suitable dispersing agent as a fabric softener in place of a quaternary ammonium compound or quat softener and would have essentially as good a softening action, and none of the disclosures mentions any specific pentaerythritol ester as a fabric softening agent nor does any mention any ester of an oligomer of pentaerythritol, of lower alkoxylated pentaerythritol or of an oligomer thereof as a fabric softening agent in a fabric softening composition. Thus, none of the references, either alone or in combination with any of the others, anticipates the present invention or makes it obvious.
  • the main component of the invented compositions of the present invention which is usually the only fabric softening compound in such products, other than a fabric softening clay, such as bentonite, which may also be present in them, is C l2 -C 22 (hereafter a higher) fatty acid ester of a pentaerythritol compound, which term is used in this specification to described higher fatty acid esters of pentaerythritol, higher fatty acid ester of pentaerythritol oligomers, higher fatty acid ester of lower alkylene oxide derivatives of pentaerythritol and higher fatty acid esters of lower alkylene oxide derivatives of pentaerythritol oligomers.
  • Pentaerythritol compound may be abbreviated as PEC herein, which description and abbreviation may apply to any or all of pentaerythritol, oligomers, thereof and alkoxylated derivatives thereof, as such or as the esters, as will be indicated by the context.
  • the oligomers of pentaerythritol are preferably those of two to five pentaerythritol moieties, more preferably 2 or 3, with such moieties being joined together through single etheric bonds.
  • the lower alkylene oxide derivatives thereof are preferably of ethylene oxide or propylene oxide monomers, dimers or polymers, which terminate in hydroxyls and are joined to the pentaerythritol or oligomer of pentaerythritol through etheric linkages.
  • At least one of the PEC OH groups and preferably at least two thereof will be esterified by a higher fatty acid or other higher aliphatic acid, which can be of an odd number of carbon atoms.
  • the higher fatty acid esters of the pentaerythritol compounds are preferably partial esters and more preferably there will be at least two free hydroxyls thereon after esterification (on the pentaerythritol, oligomer or alkoxyalkane groups).
  • the number of such free hydroxyls is two or about two but sometimes it may be one, as in pentaerythritol tristearate, or as many as eight, as in pentapentaerythritol tetrapalmitate.
  • the higher aliphatic or fatty acids that are employed as esterifying acids are those of carbon atom contents in the range of 12 to 22 and preferably 12 to 18, e.g., lauric, myristic, palmitic, oleic, stearic and behenic acids. Such may be mixtures of such fatty acids, obtained from natural sources, such as coco fatty acid, commercial stearic acid, tallow acid or hydrogenated tallow acid. Intermediate synthetic acids of odd or even numbers of carbon atoms may also be employed. Of the fatty acids lauric and stearic acids are often preferred, somethimes depending on the pentaerythritol moiety esterified.
  • the PECs utilised in this invention have some fabric softening effects but such activities are remarkably increased when a suitable dispersing agent for the PEC is present with it.
  • the PEC may be substantially insoluble and undispersed in wash water or in rinse water, in which, if dispersed, it could be conveniently applied to laundry to be softened.
  • the PEC When undispersed the PEC could be in solid agglomerate form when cold or in molten form when hot, in neither of which states does it act as effectively to soften fabrics (and in both of which cases it can deposit objectionably on treated materials to produce somewhat greasy spotting thereof).
  • Suitable dispersing agents include emulsifiers, usually employed to "solubilise” or disperse the PEC in aqueous liquid compositions that are intended to be employed as rinse cycle softeners (although they may also be added to the wash water), and solids of small (often micron size) ultimate particle sizes, such as clays, which may be present in particulate and other products, and in liquid products, too.
  • emulsions (which term herein is also intended to refer to dispersions and suspensions in liquid media, as well as to microemulsions [and sometimes solutions may be present, too, in which solvents are the "dispersing agents"]) of this invention will normally be aqueous emulsions in which the aqueous phase is the continuous phase, with the pentaerythritol compound being in the dispersed phase.
  • solvents and cosolvents such as ethanol, isopropanol, propylene glycol and various mono- and di-lower alkyl esters of diethylene glycol (Carbitols®) may also be present in such emulsions and microemulsions to promote formations of stable products, and may also be in the continuous media or solutions.
  • solvents and cosolvents such as ethanol, isopropanol, propylene glycol and various mono- and di-lower alkyl esters of diethylene glycol (Carbitols®) may also be present in such emulsions and microemulsions to promote formations of stable products, and may also be in the continuous media or solutions.
  • emulsifiers can be employed, and many such are described in the various Detergents and Emulsifiers publications of John W. McCutcheon, issued annually, particularly those for 1969, 1973, 1980 and 1981.
  • Preferred such emulsifiers are those which are alkyl ethers or amines which contain one or more hydroxyalkyl substituents too.
  • alkyl dialkanolamines or alkyl trialkanolpropylenediamines wherein the alkanol moieties are of 2 to 4 carbon atoms, preferably being 2 or 3 and more preferably being 2, and the alkyl poly(ethylene oxide) ethers are of 2 to 24 ethylene oxide units, preferably of 8 to 12 ethylene oxide units, in which emulsifiers the alkyl is of 8 to 24, preferably 12 to 18 carbon atoms. More preferred such emulsifiers are: stearyl diethanolamine, available from Hoechst A.G. as Genamin® S-020; tallow triethanol propylenediamine, available from CECA, S.A. as Dinoramox® S3; and R-O-(CH 2 CH 2 O) 10 H, wherein R is a mixture of C 12-15 alkyls, available from Hoechst A.G. as Genapol® OH-100.
  • the dispersing agent for the active pentaerythritol compound softening agent may be any suitable such particulate or powder material that is compatible with the mentioned softening agent, and can contribute some fabric softening action to the composition.
  • a material is bentonite but other fabric softening clays and clay-like materials may be substituted for it, at least in part.
  • substantially water insoluble dispersing agents may be utilised and such, like calcium carbonate and silica, may be carriers for the PEC, and even water soluble carriers, such as sodium sulfate and other "filler salts" may be used, at least in part with the dispersing agent, and sometimes can act as dispersing agents, too.
  • the bentonite employed should preferably be of a type which is gel forming in water and capable of softening fibrous materials, and should be of micron range ultimate particle size, although it may be agglomerated to larger sizes, usually in the range of 8 to 140 sieves, U.S. Sieve Series (which have openings 2.38 to 0.105 mm across).
  • an emulsifier may be utilised in the particulate or solid compositions, and bentonite, or other dispersing clays may be present in the emulsions or dispersions, or other swelling clays may be used.
  • the PEC will be employed without the presence of any other fabric softening material (except clay, such as bentonite, montmorillonite or other smectite) but it is possible to utilise such other materials with it if in the proportions and quantities employed they are not ecologically unacceptable and if they so not interfere with the fiber softening action of the PEC.
  • the concentration for 50% effect is less than 1 mg/l for quaternary ammonium compounds or quats, such as ditallowalkyl dimethyl ammonium chloride, and that is often unacceptable, environmentally.
  • quaternary ammonium compounds or quats such as ditallowalkyl dimethyl ammonium chloride
  • antistats and fabric softeners include: higher alkyl neoalkanamides, e.g.
  • N-stearyl neodecanamide N-stearyl neodecanamide; isostearamides; amines, such as N,N-ditallowalkyl N-methyl amine; amidoamines; imidazolines; di-higher fatty acid esters of di-lower alkanolamines, such as dicoco acid ester of diethanolamine; silicones; alkoxylated silicones; and clays, e.g., bentonites and other montmorillonites; and representative examples of some of such classes of such compounds are given below.
  • amines such as N,N-ditallowalkyl N-methyl amine
  • amidoamines imidazolines
  • di-higher fatty acid esters of di-lower alkanolamines such as dicoco acid ester of diethanolamine
  • silicones alkoxylated silicones
  • clays e.g., bentonites and other montmorillonites
  • compositions include the usual adjuvants that normally are present in other fabric softening compositions (including softergents), such as perfumes, fixatives, solvents, cosolvents, hydrotropes, antioxidants, stabilisers, pH adjusters, buffers, biodegradable antimicrobials, builders, fillers, enzymes, thickeners and fluorescent brighteners, all of which are known classes of materials in the fabric softening compositions field, with examples of several of these being given in the art mentioned in this specification.
  • adjuvants that normally are present in other fabric softening compositions (including softergents)
  • perfumes fixatives, solvents, cosolvents, hydrotropes, antioxidants, stabilisers, pH adjusters, buffers, biodegradable antimicrobials, builders, fillers, enzymes, thickeners and fluorescent brighteners, all of which are known classes of materials in the fabric softening compositions field, with examples of several of these being given in the art mentioned in this specification.
  • the last component of the present compositions which is required in the aqueous emulsions, is water.
  • any clean water can be employed, such as any of a hardness in the range of 0 to 500 p.p.m., as CaCO 3 , but it will be preferred to use water of a hardness of no more than 150 p.p.m., more preferably less than 50 p.p.m., and most preferably the water will be deionized water that has been irradiated.
  • the invention is directed to detergent compositions (softergents) that contain the described PEC and suitable dispersing agent.
  • Such detergent compositions will contain at least one synthetic organic detergent, preferably of the anionic or nonionic type (or a mixture thereof), which may act as a dispersing agent for the PEC.
  • the anionic detergents are normally of the water soluble sulfated and/or sulfonated lipophile type, which may be designated “sulphonated", and which include lipophilic and sulf(on)ate moieties, but analogous phosph(on)ates may also be utilised.
  • synthetic anionic organic sulf(on)ated detergents those preferred are higher alkyl (preferably linear alkyl) benzene sulfonates, higher fatty alcohol sulfates, higher fatty alcohol ethoxylate sulfates, olefin sulfonates and paraffin sulfonates.
  • such compounds are water soluble alkali metal salts, such as sodium salts, and include higher fatty alkyl or other aliphatic moieties, which serve as lipophilic moieties, and which increase detergency, especially against greasy soils.
  • higher alkyl or higher aliphatic moieties will normally be of 8 to 22 carbon atoms, preferably 10 or 12 to 16 or 18 carbon atoms and more preferably, especially for the alkyl sulfates and alkylbenzene sulfonates, the alkyl moieties will be of 12 to 14 carbon atoms.
  • the higher fatty alcohol ethoxylate sulfates that are useful will normally be of 1 to 20 ethoxy groups per mol, preferably 3 to 10 or 15, e.g., 3 to 7.
  • ethylene oxide condensates with higher fatty alcohols or with alkyl phenols such as condensation products of 3 to 20, 5 to 15, 6 to 12 or 7 to 11 mols of ethylene oxide with higher fatty alcohols of 10 or 12 to 18 or 13 to 17 carbon atoms or with alkyl phenols of 7 to 10 carbon atoms in the alkyl groups, e.g., Dobanol® 25-7, Synperonic® A7, Neodol® 25-3, Neodol 25-7, Neodol 45-11, and C 13-17 alcohols condensed with 7 or 11 mols of ethylene oxide per mol.
  • water soluble builders for such detergents it is preferred to employ water soluble salts, such as sodium or potassium salts, more preferably sodium salts, and of these the carbonates, silicates, borates, bicarbonates and phosphates, more preferably polyphosphates, are preferred, such as sodium carbonate, sodium bicarbonate, sodium silicate of Na 2 O:SiO 2 ratio in the range of 1:1.6 to 1:3, preferably 1:2 to 1:3, e.g., about 1:2, 1:2.35 or 1:2.4, sodium tripolyphosphate and tetrasodium pyrophosphate, but sodium sesquicarbonate and sodium sesquisilicate may also be used, as may be the corresponding potassium and other soluble salts, when suitable.
  • water soluble salts such as sodium or potassium salts, more preferably sodium salts
  • these the carbonates, silicates, borates, bicarbonates and phosphates, more preferably polyphosphates are preferred, such as sodium carbonate, sodium bicarbonate, sodium silicate of Na
  • the zeolites especially the hydrated zeolites.
  • Such zeolites include crystalline, amorphous and mixed crystalline and amorphous zeolites of both synthetic and natural origins, which are of satisfactorily quick and sufficiently effective activities in counteracting calcium hardness ions in wash waters.
  • the zeolites employed are characterised as having high exchange capacities for calcium ions, which exchange capacity is normally from about 200 to 400 milligram equivalents of calcium carbonate per gram of the zeolite.
  • exchange capacity is normally from about 200 to 400 milligram equivalents of calcium carbonate per gram of the zeolite.
  • the zeolite will be of the formula (Na 2 O) x .
  • crystalline zeolites that are useful those preferred include Zeolites A, X and Y, with A being more preferable, and the most preferred of these is Zeolite 4A. These zeolites are preferably in finely divided state when added to the crutcher with the synthetic detergent prior to drying, and are of ultimate particle diameters in the micron range, e.g. 0.01 to 20 microns, and actual particle sizes in the range of Nos.
  • organic builders that may be utilised include organic compounds, which are often sequestrants for hardness ions.
  • organic compounds include organic acids, especially hydroxy and amino acids, such as citric and gluconic acids usually as their water soluble sodium salts, and ethylene diamine tetraacetic acid (EDTA) and nitrilotriacetic acid (NTA), also usually as their water soluble salts, e.g., sodium salts.
  • EDTA ethylene diamine tetraacetic acid
  • NTA nitrilotriacetic acid
  • sodium salts are preferred other acceptable water soluble salts of the organic builder acids may also be utilised.
  • Additional useful builders are the organo-phosphorus chelating agents, such as the Dequests®, e.g., Dequest 2046, which are manufactured by Monsanto Co.
  • the present softergents normally comprise 3 to 35% detergent, 10 to 80% builder, and 0.5 to 25% adjuvants for the particulate or solid softergents, preferably 3 to 25%, 10 to 60% and 2 to 15%, respectively, and 3 to 20%, 5 to 35% and 0.5 to 20%, respectively, for the liquid softergents (with the balance being water or most water), preferably 3 to 15%, 5 to 25% and 0.5 to 15%, respectively.
  • the percentages of PEC and dispersant are in the ranges of 1 to 25% and 0.2 to 90%, preferably being 2 to 15% and 5 to 30% for the solids and 3 to 15% and 3 to 30% for the liquids, respectively.
  • the proportions of components of the invented compositions will be those which result in stable and effective products for fabric softening applications.
  • concentration in such compositions will normally be in the range of 1 to 25%, preferably 1 to 10%, more preferably 2 to 8% and most preferably 3 to 7%, e.g. about 5 % .
  • the content(s) of emulsifier(s) will normally be in the range of 0.2 to 10%, preferably 0.4 or 0.5 to 5% and more preferably 0.7 or 1 to 3%, e.g., about 1.25 or 2%.
  • the emulsifier is made from an alkyl alkanolamine and an alkyl poly(ethylene oxide) ether
  • the proportion of the alkanolamine will desirably be equal to or greater than that of the alkyl poly(ethylene oxide) ether, preferably being of 2 to 5 times as much, e.g., about 4 times as much.
  • such percentages can be of 0.2 to 5% of the amine compound and 0 to 5% of the ether compound, preferably 0.3 to 3% and 0.1 to 2% and more preferably 0.5 to 2% and 0.2 to 1%.
  • the percentages of such emulsifiers may be 1% of the amine compound and 0.25% of the ether compound.
  • the aqueous medium or water contents of such compositions may be the balances thereof. It is to be understood that the presences of any adjuvants or supplemental components of the emulsions will be compensated for by corresponding decreases in the water contents of the compositions.
  • the total adjuvants content will be no more than 25%, preferably will be no more than 15% and in many instances will be held to a limit of 5%. None of the adjuvants, in the amounts employed, will be such as to cause unacceptable levels of toxicity which could adversely affect aquatic organisms, including fish, that inhabit lakes and streams into which there are fed washing machine rinses that included the present compositions.
  • the invented compositions may be considered to consist essentially of the named components, in the additive or softergent form, with only environmentally acceptable proportions of adjuvants being allowed to be present therein.
  • the present compositions are essentially free of quaternary ammonium compounds.
  • One suitable adjuvant is an acidifying agent, such as hydrochloric acid, which is useful to adjust pH of the emulsion or other aqueous composition to 2.5 to 5.5, preferably 2.5 to 4, e.g. 3.5.
  • an acidifying agent such as hydrochloric acid
  • hydrochloric acid a hydrochloric acid
  • the percentage of HCl (concentrated basis) or equivalent other acidifying agent present will usually be in the range of 0.01 to 0.4%, preferably 0.05 to 0.2%.
  • the percentages of PECs may be in the same ranges as given in the preceding paragraph or at least within the wider of such ranges but the powder carrier/dispersing agent may be the balance of the composition.
  • emulsifier(s) may also be present in such compositions, preferably in about the proportions previously given for the emulsions, and of course, suitable adjuvants may be present, too.
  • the invented compositions is comparatively simple but to produce applicants' desired stable emulsions (and microemulsions) a particular process is desirably followed.
  • the PEC be melted before addition to the aqueous medium and the temperature to which the PEC is raised will desirably be within 10 °C of the melting point thereof.
  • the PEC be mixed with any meltable emulsifier, especially one of lipophilic character (or more lipophilic character than another emulsifier present), such as the amine, when a mixed amine-monoether or -ethoxylated alcohol emulsifier is employed, and melted together with it, but alternatively the two meltable materials, PEC and amine, may be separately melted and added together or simultaneously to the aqueous medium (usually water), which should also be at about the same elevated temperature, about 60 °C, for example.
  • any meltable emulsifier especially one of lipophilic character (or more lipophilic character than another emulsifier present)
  • the amine when a mixed amine-monoether or -ethoxylated alcohol emulsifier is employed, and melted together with it
  • the two meltable materials, PEC and amine may be separately melted and added together or simultaneously to the aqueous medium (usually water), which should also be at about the same elevated temperature, about 60 °
  • the water employed is often desirably acidified, as by addition to it of HCl or other suitable acid, to generate a final pH in the range of 2.5 to 5.5, preferably 2.5 to 4.0, e.g., about 3.5.
  • the emulsion produced may be cooled to room temperature, with the balance of emulsifier (the monoether or ethoxylated alcohol emulsifier, in many cases) being added before or after such cooling, preferably before.
  • emulsifier the monoether or ethoxylated alcohol emulsifier, in many cases
  • the PEC prefferably, the melted PEC, at elevated temperature, will be sprayed onto a tumbling mass of the particulate agglomerated smectite or montmorillonite powder (such as bentonite) or other disperser/carrier, and will thereby be distributed throughout it evenly.
  • the mixer employed will include size reduction means to make sure that the PEC is in small enough particles so as to promote even depositions on the laundry being treated.
  • the bentonite or other disperser particles may be at room temperature when the PEC is being applied to them and the PEC will be solidified on contact with the particulate mass, usually with little agglomeration taking place, but by controlling the PEC application, the temperature and mixer speed, some agglomeration may be obtainable, when desired.
  • the softergents may be made in usual manners, with the PEC and disperser being post-added or being added at a suitable stage of the manufacturing process, taking into account that they will not be subjected to destabilising or destructive temperatures.
  • Softergents may be charged to the washing machine as if they were detergents, with the desired concentrations being in the range of 0.1 to 1%, preferably 0.1 to 0.5%, e.g., about 0.15% in the U.S.A. and about 0.5% in Europe, to compensate for different washing conditions employed.
  • a stable emulsion is made of the above formula by heating together the pentaerythritol distearate and the Genamin S-020 to 60 °C and then admixing such melted mixture with the 60 °C acidified water, after which the Genapol OX-100, also at 60 °C, is admixed with the water emulsion of pentaerythritol distearate and Genamin S-020.
  • the resulting stable acidic emulsion which is at a pH of about 3.5, is a good fabric softening composition, better in fabric softening action than a 5% aqueous emulsion or suspension of distearyl dimethyl ammonium chloride (DSDMAC), when tested against such quat, using hardened cotton terrycloth as the test fabric to be softened.
  • DSDMAC distearyl dimethyl ammonium chloride
  • the terrycloth employed is hardened by six treatments with an aqueous hardening composition that includes sodium silicate, sodium sulfate and sodium tripolyphosphate.
  • an aqueous hardening composition that includes sodium silicate, sodium sulfate and sodium tripolyphosphate.
  • the washings effected are normal washing machine washings and the rinsings are in rinse waters containing 110 ml of softening composition per 25 litres of water (0.44%, by weight), which are employed to treat 3 kg of fabric or laundry, containing the test swatches.
  • a mini-test may be carried out, using specially designed reduced scale washing and rinsing apparatuses, and it has been found that such test results are consistent with those from the full size tests.
  • the swatches are air dried in a temperature- and humidity-controlled room, while being maintained horizontal to prevent loss of the fabric softener from the fabric due to dripping. After drying the swatches are ready for softness evaluation by the jury.
  • the judges rate the swatches for softness by comparing them to a standard, which in the present case is a swatch that was treated with a softening composition that contained the same amount of DSDMAC as the amount of pentaerythritol distearate in the test composition.
  • the judge's ratings are evaluated, using statistical techniques, and final results show whether the softening compositions are equal in softening actions or whether one or the other is significantly better.
  • the experimental composition of this example is rated as better in fabric softening effect than a control composition that contained the quat (DSDMAC), whether one, five or ten cycles of washings and rinsings are used.
  • pentaerythritol dilaurate and pentaerythritol dibehenate it was found that although such compositions were useful fabric softeners, they were not as effective as pentaerythritol distearate. Also, pentaerythritol monostearate and pentaerythritol tristearate compositions, while possessing useful fabric softening properties, were not as effective in that respect as the pentaerythritol distearate.
  • the pentaerythritol ester may be the di-tallowate or di-hydrogenated tallowate, in which the esterifying acid is tallow acid(s) or hydrogenated tallow acid(s), and the results obtained will be similar. Also, when other dispersing agents, such as those described earlier in this specification, are employed with any of the mentioned PECs, effective softening is also obtained.
  • Example 1 The procedure of Example 1 is followed, with the exception that in the formula thereof the pentaerythritol distearate is replaced by tripentaerythritol tetralaurate, and it is found that the softening action of such acidic compositions, which are at pHs in the range of 2.5 to 5.5, is comparable to that of the pentaerythritol distearate composition of Example 1.
  • the tetralaurate is superior in softening action to analogues thereof wherein the ester is the tetrastearate and/or tetrapalmitate and/or tetraoleate, and it appears that such differences are related to the maintenance of a more desirable hydrophilic/lipophilic balance (HLB), inasmuch as the tripentaerythritol tetraester has fewer free hydroxyls per carbon atom than the pentaerythritol diester.
  • HLB hydrophilic/lipophilic balance
  • tripentaerythritol tetralaurate there may be substituted tripentaerythritol tetramyristate, tripentaerythritol tristearate, tripentaerythritol tritallowate, tripentaerythritol trihydrogenated tritallowate, dipentaerythritol tetrastearate, dipentaerythritol trilaurate, tetrapentaerythritol tetralaurate, pentapentaerythritol tetrastearate and pentapentaerythritol tetratallowate and various others of the pentaerythritol esters are described herein, and fabric softening similar to that of the tripentaerythritol tetralaurate will be obtainable, without the need for the presence of quat fabric softener.
  • the described emulsions are stable, the fabric softening component is satisfactorily rewettable and may aid perfume to adhere to the treated fabric, and the presence of the dispersed PEC in a softergent and in wash water prevents excessive foaming.
  • a powdered product is made by blending together the indicated pentaerythritol oligomer ester and the bentonite, and such may be agglomerated to particle size in the 10 to 100 sieve range, U.S. Sieve Series (which has openings 2.00 to 0.149 mm across) or the powder may be used as is or suspended in water, with or without the presence of emulsifying agent(s).
  • the product is employed in the rinse water, with the concentration of the PEC being the same as in Examples 1 and 2, and it is found that the composition described has fabric softening properties like those of DSDMAC compositions containing the same amount of quat as the ester content of such composition.
  • a dispersion of the tripentaerythritol tetralaurate in water may be made by mixing together 20 parts of clay, 2 parts of the pentaerythritol ester and 76 parts of water, with 2% of mixed emulsifier (the mixture of Example 1) being optional (preferred).
  • the powder, agglomerate or emulsions of this example may be incorporated into any suitable particulate detergent composition to make a softergent for use in the wash water, or the liquid may be mixed with liquid detergent composition to make a liquid softergent for use in washing.
  • One may also employ the preparations in both the rinsing and washing operations, which is often highly desirable.
  • pentaerythritol distearate and pentaerythritol dipalmitate are PECs that best represent the most effective, most readily available and most practicable (from a commercial viewpoint) of these fabrics softeners in the described compositions.
  • the fabric softening effects described can also be obtained when the emulsifiers employed are changed and when the proportions of fabric softening compound(s) and emulsifier(s) are changed, within the ranges mentioned in this specification.
  • various other emulsifiers mentioned herein and in the McCutcheon publications, referred to previously, may be substituted for those of the present examples and the favourable results reported will be obtained.
  • aesthetic and functional adjuvants may be present, such as perfumes, brighteners and others of the various adjuvants that were mentioned previously, and the desired softening results are still obtainable.
  • compositions which are devoid of quaternary ammonium compound fabric softener, the acknowledged most effective fabric softener presently known and in use, are fabric softening compositions of essentially equal softening effectiveness (or nearly equal effectiveness in some cases) and do not possess the undesirable properties of the quats (especially persistent toxicity vs. aquatic organisms and an objectionable reactivity with anionic compounds), so they can be used when and where quats are unacceptable.
  • quats especially persistent toxicity vs. aquatic organisms and an objectionable reactivity with anionic compounds
  • the particulate detergent composition described is made by roll drying (although spray drying can also be used) a crutcher mix of various heat stable components, followed by mixing the particulate product resulting with other powdered or particulate materials, which can be those that are less heat resistant, and then perfuming the product.
  • a crutcher mix of various heat stable components, followed by mixing the particulate product resulting with other powdered or particulate materials, which can be those that are less heat resistant, and then perfuming the product.
  • the crutcher mix the components will usually be admixed with the water and any sodium hydroxide that might be present, after which the other components will be admixed in known manner so as to obtain the best mixing, following known mixing procedures.
  • the base beads made by the drying process are then blended with other components, such as perborate, clay (montmorillonite), preferably bentonite, which may be in the calcium, sodium or other swellable form, enzyme(s), hydroxylamine sulfate, sodium aluminosilicate and tetraacetyl ethylenediamine, and then the mix may be perfumed.
  • perborate clay (montmorillonite), preferably bentonite, which may be in the calcium, sodium or other swellable form, enzyme(s), hydroxylamine sulfate, sodium aluminosilicate and tetraacetyl ethylenediamine
  • the finished particulate softergent may then be packaged and marketed. When tested, it shows a surprising improvement over softergents that are based on either clay fabric softener alone or on PEC alone as the fabric softening component thereof and in comparative softening tests the invented composition scores higher than the best commercial softergent on the market. Similar desirable improvements in fabric softening detergent composition is based on carbonate/zeolite built nonionic detergent formulations and when liquid built detergents are those tested.
  • cotton terrycloth swatches are washed in an automatic washing machine in a 60 °C wash water containing 0.5% of a softergent composition of the formula of Example 4, rinsed and dried.
  • Other such swatches are washed in conventional detergent compositions, which may be of the same formula except for the omission of the bentonite and PEC, which are replaced by inert filler (sodium sulfate), and are then rinsed (in the last rinse), with rinse water to which any quaternary ammonium or amine salt rinse cycle fabric softening composition has been added, such as dimethyl distearyl ammonium chloride, so that the rinse water contains about 0.05% (or more) of the fabric softening quat or amine, and such swatches are dried.
  • conventional detergent compositions which may be of the same formula except for the omission of the bentonite and PEC, which are replaced by inert filler (sodium sulfate), and are then rinsed (
  • Strips are cut of swatches subjected to these different treatments and are tested for water absorption, by dipping lower ends of such vertical strips into an aqueous solution of water soluble dye (red Iragon) and measuring the heights to which the water rises, after 30 seconds, 1 minute, 3 minutes and 5 minutes.
  • the strips washed with the invented softergent absorb water to heights that are about twice those for the strips from the swatches that are washed, as described, and then treated with the rinse cycle softener.
  • the invented softergents soften the cotton (and other fabrics) about as well as the quat rinse cycle softening compositions, which is an exceptional result.
  • the results of these tests and similar absorption tests on towelling and clothing are important because they show that fabrics treated with the invented compositions, instead of commercial quat-based products, are more capable than such products of absorbing water (which is important for towels) and body sweat (which is important for clothing items, such as underwear, T-shirts and sport apparel).
  • the fabric softening can be increased from essentially nothing to excellent when such a dispersing agent is present with the PEC.
  • the softening action may be increased from fair to excellent, due to the presence of the dispersant. Such increase is significantly more than any expected increase due to any fabric softening properties the dispersant might possess.
  • PEC may be of fabric softening activity without the presence of the dispersing agent, such action is significantly and unexpectedly increased by the presence of such dispersant, which thereby increases the importance of the invention.
  • the invention has been described with respect to various working examples and embodiments but it is not to be considered to be limited to those because one of skill in the art, with the present specification before him or her, will be able to utilise substitutes and equivalents without departing from the scope of the invention as defined by the appended claims.

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Claims (5)

  1. Composition de détergent, comprenant un adoucissant pour le linge, pour application sur des matériaux fibreux, de telle sorte qu'un composant adoucissant pour le linge est déposé sur les matériaux fibreux et les adoucit, comprenant un PEC, qui est un composant adoucissant pour le linge qui est un ester d'acide aliphatique en C8-C24 du pentaérythritol, d'un oligomère du pentaérythritol, d'un dérivé d'oxyde d'alcoylène inférieur, contenant 1 à 10 parties d'oxyde d'alcoylène, du pentaérythritol, ou d'un dérivé d'oxyde d'alcoylène inférieur, contenant 1 à 10 parties d'oxyde d'alcoylène, d'un oligomère du pentaérythritol, ou un mélange de ceux-ci, un agent dispersant pour le PEC, un détergent organique synthétique, et un adjuvant de détergent, cette composition étant essentiellement exempte de composé d'ammonium quaternaire adoucissant pour le linge, ou d'autres composés d'ammonium quaternaire, l'agent dispersant étant un émulsionnant ou une argile adoucissante pour le linge, la composition contenant 3 à 35% en poids de détergent, 5 à 80% en poids d'adjuvant de détergent, 0,5 à 25% en poids d'additifs, 1 à 25% en poids de PEC et 0,2 à 90% en poids d'un agent dispersant.
  2. Composition suivant la revendication 1, comprenant un détergent synthétique anionique ou non ionique ou un mélange de ceux-ci.
  3. Composition liquide aqueuse de détergent suivant la revendication 1 ou 2, contenant 3 à 15% de détergent, 5 à 25% d'adjuvant de détergent, 0,5 à 15% d'additif(s), 3 à 15% de PEC et 3 à 30% d'émulsionnant.
  4. Composition particulaire suivant la revendication 1 ou 2, contenant 3 à 35% de détergent, 10 à 80% d'adjuvant de détergent, 0,5 à 25% d'additif(s), 2 à 15% de PEC et 5 à 30% d'argile adoucissante pour le linge.
  5. Composition suivant l'une quelconque des revendications 1, 2 et 4, dans laquelle l'agent dispersant est une argile adoucissante pour le linge et dans laquelle ne se trouve aucun composé d'ammonium quaternaire.
EP92306451A 1991-09-06 1992-07-14 Compositions adoucissantes pour le linge à base d'un composé de pentaérythritol et d'un agent dispersant pour un tel composé Expired - Lifetime EP0530959B1 (fr)

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US5332513A (en) * 1990-01-09 1994-07-26 Colgate-Palmolive Co. Particulate fabric softening and detergent compositions
FI921148A (fi) * 1991-09-06 1993-03-07 Colgate Palmolive Co Tygmjukgoerande produkter baserade pao en kombination av en pentaerytritolfoerining och bentonit
DE4301459A1 (de) * 1993-01-20 1994-07-21 Huels Chemische Werke Ag Wäßriges Weichspülmittel für die Behandlung von Textilien
JP3181432B2 (ja) * 1993-06-18 2001-07-03 花王株式会社 液体柔軟仕上剤組成物
DE4437032A1 (de) * 1994-10-17 1996-04-18 Henkel Kgaa Textile Weichmacher-Konzentrate
DE19623764A1 (de) * 1996-06-14 1997-12-18 Henkel Kgaa Wäßriges Wäscheweichspülmittel mit hohem Zeta-Potential
AU2004200424B2 (en) * 1998-09-23 2005-09-15 Colgate-Palmolive Company Fabric softening compositions containing pentaerythritol esters, bentonite and polyphosphonate
EP1115823B1 (fr) * 1998-09-23 2002-11-27 Colgate-Palmolive Company Compositions d'assouplissant pour tissu contenant des esters de pentaerythrol, de la bentonite et du polyphosphonate
WO2015198829A1 (fr) * 2014-06-27 2015-12-30 花王株式会社 Composition d'agent de traitement textile
JP6046084B2 (ja) * 2014-06-27 2016-12-14 花王株式会社 繊維製品処理剤組成物
JP6046085B2 (ja) * 2014-06-27 2016-12-14 花王株式会社 繊維製品処理剤組成物
CN111517992B (zh) * 2020-05-28 2021-10-01 陕西科技大学 一种对称型长链羧基表面活性剂及其制备方法和应用
CN114159318B (zh) * 2021-12-07 2023-06-23 浙江森马服饰股份有限公司 一种具有表皮保湿和舒缓作用的润肤乳及其制备方法

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JPH0247362A (ja) * 1988-08-03 1990-02-16 Kao Corp 柔軟仕上剤
EP0494769A2 (fr) * 1991-01-09 1992-07-15 Colgate-Palmolive Company Compositions adoucissantes biodégradables pour le liage à base d'esters de pentaérythritol et exemptes de composés d'ammonium quaternaires

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US4126562A (en) * 1976-06-04 1978-11-21 The Procter & Gamble Company Textile treatment compositions
EP0243735A2 (fr) * 1986-04-14 1987-11-04 Henkel Kommanditgesellschaft auf Aktien Adoncissant aqueux concentré pour matières textiles
JPH0247362A (ja) * 1988-08-03 1990-02-16 Kao Corp 柔軟仕上剤
EP0494769A2 (fr) * 1991-01-09 1992-07-15 Colgate-Palmolive Company Compositions adoucissantes biodégradables pour le liage à base d'esters de pentaérythritol et exemptes de composés d'ammonium quaternaires

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PT100302B (pt) 1999-06-30
BR9202075A (pt) 1993-04-06
KR100253468B1 (ko) 2000-04-15
ZA921990B (en) 1993-09-20
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ATE172236T1 (de) 1998-10-15
PT100302A (pt) 1993-07-30
AU1300592A (en) 1993-03-11
CA2076716A1 (fr) 1993-03-07
IE922304A1 (en) 1993-03-10
JPH05156572A (ja) 1993-06-22
DE69227293D1 (de) 1998-11-19
GR1001517B (el) 1994-02-28
NO921035L (no) 1993-03-08
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MY131270A (en) 2007-07-31
FI921147A (fi) 1993-03-07

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